US3322510A - Process for the preparation of metallic nitrides - Google Patents

Process for the preparation of metallic nitrides Download PDF

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Publication number
US3322510A
US3322510A US348405A US34840564A US3322510A US 3322510 A US3322510 A US 3322510A US 348405 A US348405 A US 348405A US 34840564 A US34840564 A US 34840564A US 3322510 A US3322510 A US 3322510A
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nitriding
uranium
hydriding
nitrogen
rare earth
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Expired - Lifetime
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US348405A
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English (en)
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Anselin Francois
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/063—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with one or more actinides, e.g. UN, PuN
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/14—Etching locally
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles

Definitions

  • This invention relates to a process and apparatus for the practical application of said process for the preparation of metallic nitrides which are intended for subsequent sintering and more especially for the preparation of nitrides of metals of the transuranic group, of the rare earth metals and of yttrium.
  • the intermediate product was heretofore obtained by causing ammonia gas or nitrogen to react at suitable temperatures with uranium hydride UH or with uranium metal in the finely divided state, all attempts at nitriding of massive uranium having failed.
  • the metal is covered when heated in nitrogen with an adhesive layer of mononitride UN and sesquinitride U N the reaction practically coming to an end as soon as the layer has reached a certain depth.
  • the nitrides of the rare earth metals are usually obtained as a result of the action of nitrogen or ammonia gas, either on said metals in the divided state or on the hydrides of these metals.
  • the divided metals readily react with oxygen, with the resulting danger that the nitrides obtained can very frequently be contaminated by this element. Consequently, it is preferable to start from the hydride as in the case of uranium, since hydrogen reacts with the metal so as to produce a powdered hydride which is then transformed into nitride as a result of the action of nitrogen or of ammonia gas.
  • the uranium metal powders which are obtained, for example, from U0 by thermal reduction process contain impurities such as, for example, oxides and traces of organic stabilizers, thereby giving rise to dangers of carburization.
  • the main arrangement of the invention is precisely intended to overcome the disadvantages attached to the prior art processes which have just been mentioned.
  • the process in accordance with the invention is characterized in that it consists in carrying out the nitriding operation on massave elements of metal previously subjected to a surface hydriding which facilitates the initiation and development of said nitriding operation towards the center of said elements.
  • the process applies more especially to the metals of the transuranic group, to the rare earth metals and to yttrium.
  • the metallic elements employed can have a number of different configurations such as rods, plates, ingots, lumps or pellets, etc., namely which have a massive appearance in contradistinction to any definition in the form of grains or metallic powders.
  • FIGS. 1 and 2 show diagrammatically and respectively a general view of the equipment employed and a vertical cross-section of a nitriding crucible together with accessories.
  • the elements 1 of uranium are placed inside a vessel 2 of stainless steel or of Monel metal which is in turn placed inside a furnace 3.
  • the vessel 2 is closed by a cover 4 which is applied against a flange 5 forming one piece with said vessel, air-tightness being achieved by means of a gasket 6, for example of neoprene, which is compressed by means of screws 7 which are screwed through the cover and applied against the flange.
  • the cooling of the gasket 6 is carried out indirectly by means of a water circulation system S which cools the cover 4, said cover being in contact with said gasket 6.
  • a vacuum is created inside the vessel 2 by means of a pump set 11.
  • the pump set 11 is then isolated by means of the valve 12 and the apparatus is then filled by means of a surge tank 13 fitted with a pressure gauge 14 with hydrogen which has been passed through a drying column 15 normally isolated by means of a valve 16 with a view to eliminating any trace of moisture.
  • the installation can advantageously be purged a number of times with hydrogen prior to filling the apparatus with a limited quantity of hydrogen at a pressure which can be slightly in excess of atmospheric pressure.
  • valve 16 is then finally closed and the temperature is brought up to approximately 230 C.; at the end of a certain period of time which is usually less than one hour,
  • the nitriding operation is then carried out, preferably by making use of the same installation, thereby avoiding any handling and any danger of oxidation. To this end, it is merely necessary to provide the installation with a continuous supply of nitrogen under a pressure of l to 3 bars as processed through a drying column 17 which is normally isolated by a valve 18.
  • the temperature is progressively brought up to the vicinity of 400 C., the speed of reaction between the uranium and the nitrogen then becoming appreciable.
  • the nitride is detached from the metal in the form of flakes.
  • the surface of the metal is thus continuously renewed and the reaction can continue towards the center of the metallic element which is thus undergoing treatment.
  • the uranium lumps are preferably placed on a wide-mesh grid 19 which is not an essential feature but which nevertheless prevents the packing of flakes around the metal which would be liable to result in a slowing-down of the nitriding reaction.
  • the reaction can accordingly be considered as completed at the end of a few hours, when the pressure no longer falls inside the apparatus if the valve 18 is shut off for a certain period of time.
  • the vessel 2 is then isolated by means of the valve 9 and separated from the remainder of the installation by means of the three-piece union so as to permit of all subsequent handling operations such as, for example, the transfer of said vessel into a glove box.
  • the metals of the transuranic group, the rare earth metals and yttrium can be subjected directly to the action of a mixture of hydrogen and nitrogen.
  • the start of the reaction is found to take place as a result of a pressure drop and, from this moment, it is merely necessary to ensure a continuous supply of nitrogen in order that the reaction should continue in the normal manner. Accordingly, in the case of uranium, it is possible to introduce a mixture of hydrogen and nitrogen in the cold state and under pressure while bringing the temperature from the outset to 400 C.
  • the uranium nitride which is obtained is in the form of brittle laminae or flakes, the color of which ranges from black to ash grey. Said product is extremely active, is sensitive to traces of oxygen and of moisture and ignites spontaneously in contact with air. A crushing operation produces a black powder of fine and uniform particle size and having a metallic luster.
  • This product is highly reproducible under given processing conditions, while the composition thereof varies between UN and UN X-ray diffraction shows that said product is a solid solution of sesquinitride and dinitride UgUg-UN which exhibits a crystalline structure of the fluorine type, that is to say a face-centered cubic structure.
  • the intermediate product thus obtained is employed for the purpose of preparing the mononitride which, in the case of uranium mononitride which is more especially contemplated, can be utilized as a nuclear fuel.
  • the compound UN is dissociated in vacuo starting from 800 C.
  • the stoichiometric mononitride UN thus obtained is completely free of impurities, and is a compound which is suitable for sintering.
  • the process in accordance with the invention also permits the possibility of nitriding plutonium.
  • Massive elements of plutonium which are subjected as a preliminary treatment to a surface hydriding are preferably nitrided at 350 C.
  • the nitriding of plutonium results directly in the production of the mononitride PuN as shown by the X-ray diffraction spectrum of the final product.
  • the process can be carried out in a similar manner or else by first performing a hydriding treatment, followed by a nitriding treatment.
  • the second mode of operation is to be preferred, however, in the case of large samples of rare earth metals having a low melting point such as, for example, lanthanum.
  • a low melting point such as, for example, lanthanum.
  • the quantities of heat evolved by the hydriding and nitriding reactions being added to each other, thus resulting in a melting of the metal at the center itself of the element which it is desired to nitride, thereby entailing the risk of causing the rupture of the surface layer of hydride which holds the molten mass and forms a crust around the element.
  • this danger does not exist since the mass of molten metal is too small to bring about the rupture of the layer of hydride.
  • the nitriding stage can comprise a crushing operation if it is desired to accelerate the nitriding process.
  • the process is carried out on metallic elements of rare earths and yttrium which have relatively high melting points, and the samples on which the process is performed have a weight of the order of 50 grams.
  • said elements After having been subjected to a thorough mechanical cleaning treatment, said elements are heated in a first stage to a temperature which varies between 600 and 800 C. in an atmosphere containing one volume of hydrogen and 5 volumes of nitrogen at a pressure which can vary between 1 and 5 bars over a period of time which is less than 5 hours.
  • a nitriding rate i.e., the percentage of metallic element nitrated, the m-ononitrate of uranium UN corresponding to a rate of nitration of 1, which can range from 0.85 to 0.95.
  • the said metallic elements are then subjected after cooling to a crushing operation.
  • the pieces obtained are brought in a second stage to approximately 800 C. for a period of ten hours, all other conditions of operation being the same as before.
  • the starting material employed consists of laminated elements, there is directly obtained without any preliminary crushing stage a nitriding rate which is equal to 1.
  • Example 1 Provision is made for 600 grams of uranium in the form of cylindrical rods 3 centimeters in diameter which are placed inside a vessel, the volume of which is equal to 1 liter and which communicates with a surge tank, the volume of which is also equal to 1 liter; after having purged the apparatus, 3 liters of hydrogen are fed in so as to bring the pressure up to approximately 1.5 bar and the temperature is brought to 230 C.; after minutes the pressure has dropped to 1 bar, which indicates that a surface hydriding process has taken place; from this moment, nitrogen is fed in continuously at a pressure of 2 bars for a period of 10 hours, the temperature being maintained at 400 C.; the product obtained under these conditions corresponds to UN By dissociation in vacuo at a temperature which is greater than or equal to 800 C., mononitride is thus obtained and is then sintered under the usual conditions.
  • Example 2 In a similar apparatus, there are placed grams of plutonium in the form of a small cylindrical rod 2.5 centimeters in length and 8 millimeters in diameter; in this case, the nitriding process is carried out at 350 C. and directly results in the production of mononitride in the form of agglomerated flakes.
  • Example 3 Provision is made for 50 grams of lanthanum as starting material, the sample is cleaned mechanically in oil then washed with acetone. The surface of the sample is thus endowed with a high luster.
  • the sample is placed in the nitriding vessel.
  • the vessel is heated so that the temperature rises by 500 C. in minutes while hydrogen is introduced in small quantities in such manner as to develop a pressure of 1.5 bars within the interior of the vessel.
  • hydrogen is introduced in small quantities in such manner as to develop a pressure of 1.5 bars within the interior of the vessel.
  • the reaction lasts for a total period of 45 seconds and then the pressure within the vessel falls to 0.5 bar.
  • Nitrogen is then introduced until a pressure of 4 bars is developed within the vessel. There is immediately noticed an increase in temperature. After two hours of nitriding, the vessel is allowed to cool. A nitriding rate is thus obtained which is equal to 0.92.
  • Example 4 There is employed as starting material a sample of lanthanum having a weight of approximately 10 grams and provided in the form of a thin plate having a thickness of 2 to 3 millimeters.
  • the nitriding process takes place in this case in a single stage, the crushing operation being dispensed with.
  • the nitriding rate obtained is equal to 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US348405A 1962-07-04 1964-03-02 Process for the preparation of metallic nitrides Expired - Lifetime US3322510A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR902971A FR1335556A (fr) 1962-07-04 1962-07-04 Perfectionnements apportés aux procédés et appareils pour la préparation de nitrures métalliques susceptibles d'être frittés ultérieurement, notamment ceux de l'uanium
FR926513A FR83185E (fr) 1962-07-04 1963-03-01 Perfectionnements apportés aux procédés et appareils pour la préparation de nitrures métalliques susceptibles d'être frittés ultérieurement, notamment ceux de l'uranium

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US (1) US3322510A (da)
BE (2) BE644550A (da)
CH (2) CH415573A (da)
DE (2) DE1267202B (da)
DK (1) DK115838B (da)
FR (1) FR83185E (da)
GB (2) GB997446A (da)
LU (2) LU43926A1 (da)
NL (2) NL6402031A (da)
SE (1) SE304982B (da)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953355A (en) * 1974-05-29 1976-04-27 The United States Of America As Represented By The United States Energy Research And Development Administration Preparation of uranium nitride
US4029740A (en) * 1975-11-24 1977-06-14 Rockwell International Corporation Method of producing metal nitrides
WO1993000626A1 (en) * 1991-06-27 1993-01-07 Teledyne Industries, Inc. System for controlled nitriding
US5188810A (en) * 1991-06-27 1993-02-23 Teledyne Industries, Inc. Process for making niobium oxide
US5211921A (en) * 1991-06-27 1993-05-18 Teledyne Industries, Inc. Process of making niobium oxide
US5234674A (en) * 1991-06-27 1993-08-10 Teledyne Industries, Inc. Process for the preparation of metal carbides
US5284639A (en) * 1991-06-27 1994-02-08 Teledyne Industries, Inc. Method for the preparation of niobium nitride
US5322548A (en) * 1991-06-27 1994-06-21 Teledyne Industries, Inc. Recovery of niobium metal
US20040007292A1 (en) * 2002-07-15 2004-01-15 Hideto Fujita Method and apparatus for dynamic nitriding
JP2012056834A (ja) * 2010-08-11 2012-03-22 Taiheiyo Cement Corp 金属窒化物の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534676A (en) * 1945-02-16 1950-12-19 Amos S Newton Preparation of compounds of uranium and nonmetals
US2544277A (en) * 1945-06-12 1951-03-06 Amos S Newton Preparation of uranium nitride
US2776874A (en) * 1954-06-25 1957-01-08 Republic Steel Corp Reactor for the high temperature reduction of iron oxide and the like
US3180702A (en) * 1962-12-04 1965-04-27 United Nuclear Corp Process for preparing uranium nitride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534676A (en) * 1945-02-16 1950-12-19 Amos S Newton Preparation of compounds of uranium and nonmetals
US2544277A (en) * 1945-06-12 1951-03-06 Amos S Newton Preparation of uranium nitride
US2776874A (en) * 1954-06-25 1957-01-08 Republic Steel Corp Reactor for the high temperature reduction of iron oxide and the like
US3180702A (en) * 1962-12-04 1965-04-27 United Nuclear Corp Process for preparing uranium nitride

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953355A (en) * 1974-05-29 1976-04-27 The United States Of America As Represented By The United States Energy Research And Development Administration Preparation of uranium nitride
US4029740A (en) * 1975-11-24 1977-06-14 Rockwell International Corporation Method of producing metal nitrides
WO1993000626A1 (en) * 1991-06-27 1993-01-07 Teledyne Industries, Inc. System for controlled nitriding
US5188810A (en) * 1991-06-27 1993-02-23 Teledyne Industries, Inc. Process for making niobium oxide
US5211921A (en) * 1991-06-27 1993-05-18 Teledyne Industries, Inc. Process of making niobium oxide
US5234674A (en) * 1991-06-27 1993-08-10 Teledyne Industries, Inc. Process for the preparation of metal carbides
US5284639A (en) * 1991-06-27 1994-02-08 Teledyne Industries, Inc. Method for the preparation of niobium nitride
US5322548A (en) * 1991-06-27 1994-06-21 Teledyne Industries, Inc. Recovery of niobium metal
US20040007292A1 (en) * 2002-07-15 2004-01-15 Hideto Fujita Method and apparatus for dynamic nitriding
JP2012056834A (ja) * 2010-08-11 2012-03-22 Taiheiyo Cement Corp 金属窒化物の製造方法
US20130129600A1 (en) * 2010-08-11 2013-05-23 Taiheiyo Cement Corporation Method for producing metal nitride
US9302913B2 (en) * 2010-08-11 2016-04-05 Taiheiyo Cement Corporation Method for producing metal nitride

Also Published As

Publication number Publication date
GB1049504A (en) 1966-11-30
CH449593A (fr) 1968-01-15
NL294900A (da)
FR83185E (fr) 1964-06-26
SE304982B (da) 1968-10-14
BE644550A (da) 1964-06-15
DE1261839B (de) 1968-02-29
DE1267202B (de) 1968-05-02
BE634503A (da)
LU45557A1 (da) 1964-04-29
CH415573A (fr) 1966-06-30
LU43926A1 (da) 1963-08-19
GB997446A (en) 1965-07-07
DK115838B (da) 1969-11-17
NL6402031A (da) 1965-06-25

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